DE1218211B - Insecticidal preparations - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

AOIn

German KL: 451-9 / 36

Number: 1218 211

File number: C 34736IV a / 451

Filing date: December 23, 1964

Opening day: June 2, 1966

The present invention relates to insecticides Preparations which are characterized by a content of about 1 to 10 parts by weight of O, O-dimethyl - O - (3 - methyl - 4 - nitrophenyl) - phosphorothioate and about 1 part by weight of O, O-dimethyl-O- (2,2-dichlorovinyl) -phosphate as essential active ingredients. It also relates to insecticidal preparations, obtained by mixing 0,0-dimethyl-O - (3 - methyl - 4 - nitrophenyl) - phosphorothioate, O, O-dimethyl-O- (2,2-dichlorovinyl) phosphate and we- ίο at least one carrier, in some cases preferably terpene oil or conifer oil will.

The insecticidal preparations according to the invention can, for example, destroy harmful insects and in the form of contact, gas or food poisons z. B. as protection for plants, material and food be used. The new insecticidal preparations are also at increased insecticidal Effectiveness of less toxicity to plants, especially cruciferous vegetables. Other benefits can be seen from the following description.

To produce the present insecticidal preparations, O, O-dimethyl-O- (3-methyl-4-nitrophenyl) phosphorothioate is used with O, O-dimethyl-O- (2,2-dichlorovinyl) phosphate mixed in a weight ratio of 1: 1 to 10: 1.

The preparations according to the invention are effective quickly, especially if they are used as gas poison (for example as an aerosol), such as a comparison with one of the components O, O-dimethyl-O- (3-methyl-4-nitrophenyl) phosphorothioate alone shows. While the preparations show low toxicity to warm-blooded animals, they have a long-lasting toxicity irreversible effect, i.e. the pests cannot survive or spread themselves after using the preparation gradually recover.

The synergistic effect, i.e. the increased effectiveness of the present preparations, is particularly surprising; for example, the insecticidal effectiveness considerably exceeds the effectiveness of the individual Components. If the present preparations are used on insects, they are in effective at various stages of development, such as eggs, larvae and adult insects.

For example, the following substances should be treated: Liquids - such as water - in tanks, any objects in inhabited rooms, in basements, on floors, in stables, as well as furs, Feathers, wool and the like, as well as living organisms of the flora and fauna in their various forms Stages of development.

Insecticidal preparations

Applicant:

CIBA Aktiengesellschaft, Basel (Switzerland);
Sumitomo Chemical Company Ltd.,
Osaka (Japan)

Representative:

Dr.-Ing. Dr. jur. F. Redies,
Dr. rer. nat. B. Redies, Dr. rer. nat. D. Turk
and Dipl.-Ing. Ch. Gille, patent attorneys,
Opladen, Rennbaumstr. 27

Named as inventor:

Dr. Fritz Bachmann, Riehen;

Dr. Marcus v. Orelli, Münchenstein;

Dr. Ladislaus Pinter, Basel (Switzerland);

Shinichi Suzuki, Sakai-shi;

Saichiro Kuramoto, Toyonaka-shi (Japan)

Claimed priority:

Japan of December 26, 1963 (70 597),

Switzerland of April 10, 1964 (4675)

The pest control is carried out with the present preparations according to the usual methods carried out, e.g. B. by treating the objects with the present preparation in the form of a Powder or a spray, i.e. a solution or suspension in water or a suitable one Organic solvents such as alcohol, petroleum, tar distillate and the like. Aqueous solutions can also be used or aqueous emulsions obtained from an organic solution of the active preparation, Use the spray or immersion method to protect objects. Particularly favorable results is obtained when the preparation is used as an aerosol.

The spray and powder preparations can be admixed with the usual inert carriers, such as. B. Kaolin, plaster of paris or bentonite, or other ingredients, such as waste liquor, cellulose derivatives and the like, and common ones Contain wetting and adhesive agents to increase wettability and adhesion.

609 577/426

The preparation according to the invention can be in the form of a powder, an aqueous emulsion, or a paste or a self-dispersing oil.

0,0 - dimethyl - O - (3 - methyl - 4 - nitrophenyl) - phosphorothioate is a widely used compound of extremely low toxicity to warm blooded animals, of extensive effectiveness and high insecticidal activity. However, this connection is comparative toxic to vegetables and fruit trees; this tendency is particularly noteworthy in crucifera. These Compound therefore has the disadvantage that it cannot be used in crucifers, in spite of the great insecticidal effectiveness against pests of these plants, such as B. Pieris rapae, Barathra brassicae and Agrotis.

The present insecticidal preparation is now less toxic and less toxic to the plants described above has excellent insecticidal effectiveness.

As a result of extensive research, the inventors have found that the preparation by mixing equivalent amounts of 0,0-dimethyl-O- (2,2-dichlorovinyl) phosphate and 0,0-dimethyl - O - (3 - methyl - 4 - nitrophenyl) - phosphorothioate and 40 to 85 percent by weight of terpene or conifer oil - calculated on the weight of the mixture of two active substances - not just the chemical damage described above by 0,0-dimethyl - O - (3 - methyl - 4 - nitrophenyl) - phosphorothioate in vegetables and fruit trees, especially crucifers, can reduce, but that it is of extremely high insecticidal effectiveness.

This is caused by the synergistic effect, like a comparison with the individual components proves.

In this case it is preferable to use 0,0-dimethyl-O - (3 - methyl - 4 - nitrophenyl) - phosphorothioate with O, O-dimethyl-O- (2,2-dichlorovinyl) -phosphate in one Mix ratio of 1: 1.

Terpene or conifer oil is preferably added in an amount of 10 to 100 percent by weight, in particular 40 to 85 percent by weight, calculated on the weight of the mixture of Ο, Ο-dimethyl - O - (3 - methyl - 4 - nitrophenyl) - phosphorothioate and O, O-dimethyl-O- (2,2-dichlorovinyl) -phosphate.

If the mixture obtained is an emulsion, an adjuvant, such as. B. xylene, and an emulsifier be added. An anionic or nonionic surface-active agent can be used as an emulsifier Use a substance or a mixture of both.

The ingredients are mostly mixed in the manner indicated in the examples.

From an economic point of view, the preparation according to the invention is extremely inexpensive, since it is part of the expensive one O, O-dimethyl-O- (3-methyl-4-nitrophenyl) phosphorothioate by the cheap O, O-dimethyl-O- (2,2-dichlorovinyl) -phosphate is replaced and even at a much lower concentration than when using 0,0-dimethyl-0- (3-methyl-4-nitrophenyl) phosphorothioate alone the same high insecticidal effectiveness is achieved. Also the chemical damage Crucifera and the like can be reduced.

example 1

In a room of 35 m ³ , 0,0-dimethyl-O- (3-methyl-4-nitrophenyl) -phosphorothioate (A), 0,0-dimethyl-O- (2,2-dichlorovinyl) -phosphate (B ) or a mixture of the same in different weight ratios in the form of an aqueous emulsion or acetone solution with HiHe an atomizer at 2 atmospheres pressure. 250 houseflies were used for each experiment. The results are given in the following tables.

Table I.
Type of application: aqueous emulsion

Concentration, mg / cm ³ ..

House flies, killed
within

15 to 30 minutes

30 to 45 minutes

Active component

mixture
A: B = 10: 1

0.2

10
25th

2.2

63
93

Table II
Type of application: aqueous emulsion

Concentration, mg / cm ³
House flies, killed
within
0 to 15 minutes .. ".

Active component

mixture

73

A: B =

108

Table III
Type of application: acetone solution

Concentration, mg / cm ³

House flies, killed
within

0 to 15 minutes ...
15 to 30 minutes ...

Active component

mixture

A: B = 10: 1

0.2

1
33

2.2

5
76

The mixture of A and B shows a significantly reduced toxicity for warm-blooded animals compared to B.

Example 2

Depending on a l ° / _o methanolic stock solution is prepared from 0,0-dimethyl-0- (3-methyl-4-nitrophenyl) phosphorothioate (A), O, O-dimethyl-O- (2,2-dichlorovinyl) phosphate (B) and a mixture thereof; these are diluted to the desired concentration with methanol.

About 1 mg of the solution is applied to the thorax of ten test animals using a platinum wire loop brought, which are then placed in a petri dish without food.

The activity limit is measured, i.e. the minimum concentration at which 100% effectiveness is still achieved is established against the test animals.

The results are shown in the following tables.

Table IV

Effectiveness in house flies

Limit of activity (γ) ..

Active component

Mixture A: B = 3: 7

0.15

0.03

0.015

Table V

Effectiveness in American cockroaches (Periplaneta americana)

Activity limit (γ

Active component

mixture

5.0 2.5

2.0

Example 3 Example 4

The first emulsifiable concentrate, made by mixing 20 g of O, O-dimethyl-O- (3-methyl-4-nitrophenyl) phosphorothioate, 22 g xylene and 10 g of a surface-active substance, e.g. n-dodecyl mercaptopolyethylene glycol ether, and the second emulsifiable concentrate prepared by mixing 20 g of O, O-dimethyl-O- (2,2-dichlorovinyl) phosphate, 21 g

ίο conifer oil and 7 g of the same surfactant Substance, were mixed together and vigorously stirred. The emulsifiable concentrate thus produced was diluted with 800 to 1600 times its volume of water and on a crucifer applied. The emulsion showed excellent insecticidal activity against harmful insects and had no harmful effect on the plants.

A: B = 3: 7

The first emulsifiable concentrate, made by mixing 25 g of O, O-dimethyl-O- (3-methyl-4-nitrophenyl) phosphorothioate, 22 g xylene and 4 g of a surface-active substance, e.g. n-dodecyl mercaptopolyethylene glycol ether, and the second emulsifiable concentrate made by mixing 25 g of O, O-dimethyl-O- (2,2-dichlorovinyl) phosphate, 21 g Conifer oil and 3 grams of the same surfactant were combined and stirred vigorously. The emulsifiable concentrate thus produced was 1000 to 2000 times its amount Diluted by volume of water and applied to a crucifer. The emulsion showed excellent insecticidal properties Effectiveness on harmful insects and had no harmful effect on the plant.

Example 5

The first emulsifiable concentrate made by mixing 25 g of O, O-dimethyl-O- (3-methyl-4-nitrophenyl) phosphorothioate and 3.5 g of a surfactant, e.g. p-isooctylphenyl polyethylene glycol ether, and the second emulsifiable concentrate made by mixing 25 grams O, O-dimethyl-O- (2,2-dichlorovinyl) phosphate, 43 g Conifer oil and 3.5 grams of the same surfactant were mixed together and stirred vigorously. The emulsifiable concentrate thus prepared was 1000 to 2000 times its amount Diluted by volume of water and applied to a crucifer. The emulsion showed excellent insecticidal properties Effectiveness against harmful insects and did not cause chemical damage in the Plant.

Example 6

The chemical harm to crucifera is shown in the following table.

Table VI

Plant name

Preparation dilution ratio
X 500 I X 100 O IX 2000

radish

Komatsuna
(kind of Chinese
Cabbage)

Preparation according to Example 3 preparation according to Example 4 Preparation according to Example 5, a 50 ° / _o strength emulsifiable concentrate of

O, O-dimethyl-O- (3-methyl-4-nitrophenyl) -

phosphorothioate

Preparation according to Example 3 Preparation according to Example 4 Preparation according to Example 5 a 50% emulsifiable concentrate

O, O-dimethyl-O- (3-methyl-4-nitrophenyl) -

phosphorothioate

Preparation according to Example 3 Preparation according to Example 4 Preparation according to Example 5 a 50% emulsifiable concentrate

O, O-dimethyl-O- (3-methyl-4-nitrophenyl) -

phosphorothioate

The test plants had two adult leaves; ten such plants were in a pot sown with a diameter of 15 cm.

Each preparation was diluted to the specified concentration and ^{sprayed in an amount of 10 cm 3} per pot.

In Table VI above, "-" means harmlessness and "+" harmfulness. When the number "+" increases, the chemical harmfulness increases,

»±« means that the preparation is mostly harmless.

Example 7

The synergistic effect of the insecticidal effectiveness compared to the activity of the component O, O-dimethyl-O- (3-methyl-4-nitrophenyl) phosphorothioate alone and the component 0,0-dimethyl-O- (2,2-dichlorovinyl) phosphate only at Agrotis is shown below.

Table VII

Insecticidal effectiveness in the second (7o) Stage of development X 4000 by Agratis preparation 80 Dilution ratio XlOOO X 2000 50 X 8000 Preparation produced in example 3 100 100 40 50% emulsifiable concentrate from f 20th O, O-dimethyl-O- (3-methyl-4-nitrophenyl) - I. 95 80 20th phosphorothioate ( O, O-dimethyl-O- (2,2-dichlorovinyl) phosphate 90 60 0

Claims (2)

Patent claims: 1. Insecticidal agent, characterized by a content of about 1 to 10 ^{parts by weight a} 5 parts of O, O-dimethyl-O- (3-methyl-4-nitrophenyl) phosphorothioate and about 1 part by weight of O ₅ O-dimethyl-O- (2,2-dichlorovinyl) phosphate as essential active ingredients. 2. Insecticidal preparations according to claim 1, characterized by a content of terpene oil and conifer oil as a carrier. 609 577/426 5.66 © Bundesdruckerei Berlin